Treatment of textile materials



States TREATMENT or Tnx'rnn MATERIALS No Drawing. Application December 1, 1951, Serial No. 259,504

13 Claims. (Cl. 117139.4)

This invention relates to the treatment of textile materials. More particularly, the invention relates to a method for preparing textile fabrics that have improved wrinkle and shrink resistance and other improved properties.

Specifically, the invention provides a novel process for preparing crease resistant and shrink resistant, resilient textile fabrics having improved washability and no chlorine retention which comprises applying to the textile fabric a solution containing a polyepoxide and subsequently curing the polyepoxide within the fibers of the fabric in the presence of a curing agent. The invention further provides improved fabrics prepared by the aforedescribed process.

Many of the textile fabrics, such as cotton and rayon,

have rather poor resilience, i. e., they are easily creased or wrinkled when crushed or otherwise subjected to localized physical force. In addition, many of these fabrics have poor dimensional stability as exemplified by poor resistance to shrinkage. In order to overcome these shortcomings it has been common practice to treat the fabric with a resin, such as a ureaor melamine-formaldehyde resin, that could be subsequently insolubilized within fabric fibers. While this method has met with some success with colored fabrics, it has been of little or no use in the treatment of white goods that may be subjected to bleaching. It has been found that during the bleaching process, the added resins retain considerable quantities of the chlorine and when the fabric is subsequently exposed to heat as in ironing or hot-air drying, the cloth is charred or discolored and the strength of the material seriously degraded. In addition, many of the fabrics treated with these resins have poor washability, i. e., the resin is easily lost from the fabric after a few washings with soap and water.

It is an object of the invention, therefore, to provide a new method for treating textile materials. It is a further object to provide a process for rendering textile fabrics crease and shrink resistant without giving a harsh feel and undue stiffness to the fabric. It is a further object to provide a method for making fabrics more resilient. It is a further object to provide a method for preparing creaseand shrink-proof, resilient fabrics that have no chlorine retention. It is a further object to provide a method where the non-creasing and non-shrinking prop erties will be resistant to washing. It is a further object to provide a method for treating textile fabrics which, while imparting wrinkle and shrink resistance to the fabrics, has little if any detrimental effect on the other desired properties of the fabric. It is a further object to provide a method for crease-proofing of textile materials that in many cases brings about an increase in the tear strength of the fabric. It is still a further object to provide textile fabrics having many improved properties. Other objects and advantages of the invention will be apparent from the following detailed description thereof.

It has now been discovered that these and other objects may be accomplished by the novel process of the invention 2,752,269 Patented June 26, 1956 which comprises applying to the textile fabric a solution containing a polyepoxide and subsequently curing the polyepoxide within the fibers of the fabric in the presence of a curing agent. Fabrics treated in this manner, even with relatively small quantities of the polyepoxide, have excellent resistance to creasing and rubbing and still have a soft feel. The fabrics also have improved resistance to shrinkage and are quite resilient. Surprisingly, these properties are all obtained by the aforedescribed treatment with little if any loss of other desired properties, such as tear and tensile strength, which loss generally occurs with the addition of the conventional crease-proofing resins. In fact, with many of the polyepoxides it has been found that there is actually an increase in the tear strength of the treated fabric.

It has further been surprisingly found that the fabrics treated in the above-described manner have no ability to retain chlorine and the coated fabrics may be bleached or otherwise exposed to chlorine without danger of being discolored, charred or weakened during subsequent heat treatments. In addition, the fabrics have been found to have improved washability and can be washed numerous times without danger of losing any substantial amount of the polyepoxide resin.

The polyepoxides used in treating the fabrics include those organic compounds having at least two epoxy groups per molecule. The po-lyepoxides may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted if desired with noninterfering substituents, such as hydroxyl groups, ether radicals, and the like. They may also be monomeric or polymeric.

For clarity, many of the polyepoxides and particularly those of the polymeric type will be described throughout the specification and claims in terms of an epoxy equivalency. The term epoxy equivalency refers to the average number of epoxy groups contained in the average molecule. This value is obtained by dividing the average molecular weight of the polyepoxide by the epoxide equivalent weight. The epoxide equivalent weight is determined by heating a one-gram sample of the polyepoxide with an excess of pyridinium chloride dissolved in pyridine. The excess pyridiniurn chloride is then back titrated with 0.1 N sodium hydroxide to phenolphthalein end point. The epoxide value is calculated by considering one HCl as equivalent to one epoxide group. This method is used ot obtain all epoxide values reported herein.

If the polyepoxide material consists of a single compound and all of the epoxy groups are intact, the epoxy equivalency will be integers, such as 2, 3, 4, and the like. However, in the case of the polymeric-type polyepoxides many of the materials may contain some of the monomeric monoepoxides or have some of their epoxy groups hydrated or otherwise reacted and/or contain macromolecules of somewhat different molecular weight so the epoxy equivalency may be quite low and containing fractional values. The polymeric material may, for example, have an epoxy equivalency of 1.5, 1.8, 2.5 and the like.

The polyepoxides may be exemplified by the following: 1,4 bis(2,3 epoxypropoxy)benzene, 1,3 bis(2,3- epoxypropoxy)benzene, 4,4 bis(2,3 epoxypropoxy)- diphenyl ether, 1,8 bis(2,3 epoxypropoxy)octane, 1,4 bis(2,3 epoxypropoxy)cyclohexane, 4,4 bis(2 hydroxy 3,4 epoxybutoxy) diphenyldimethylmethane, 1,3 bis(4,5 epoxypentoxy) 5 chlorobenzene, 1,4- bis(3,4 epoxybutoxy) 2 chlorocyclo-hexane, diglycidyl thioether, diglycidyl ether, ethylene glycol diglycidyl ether, resorcinol diglycidyl ether, l,2,5,6-diepoxyhexyne, 1,2,5,6-

3 diepoxyhexane, and l,2,3,4-tetra(2 hydroxy 3,4 epoxybutoxy)butane.

Other examples include the glycidyl polyethers of polyhydricphenols obtained by reacting a polyhydric phenol with a great excess, e. g., 4 to 8 mol excess, of a halogen-containing epoxide in an alkaline medium. Thus, Polyether F described hereinafter, which is substantially 2,2-bis(2,3-epoxypropoxyphenyl)propane is obtained by reacting bis-phenol (2,2-bis(4-hydroxyphenyl)propane) with an excess of epichlorohydrin. Other polyhydric phenols that can be used for this purpose include resorcinol, catechol, hydroquinone, methy resorcinol, or polynuclear phenols, such as 2,2-bis(4-hydroxyphenyl)butane, 4,4 dihydroxybenzophenone, bis(4 hydroxyphenyl)ethane, and 1,5-dihydronaphthalene. The halogen-containing epoxides may be further exemplified by 3-chloro-1,2-epoxybutane, 3 bromo l,3 epoxyhexane, 3-chloro-1,2-epoxyoctane, and the like.

Still a further group of the polyepoxides comprises the polyepoxy polyethers obtained by reacting, preferably in the presence of an acid-acting compound, such as hydrofluoric acid, one of the aforedescribed halogen-containing epoxides with a polyhydric alcohol, and subsequently treating the resulting product with an alkaline component. Polyhydric alcohols that may be used for this purpose include glycerol, propylene glycol, ethylene glycol, diethylene glycol, butylene glycol, hexanetriol, sorbitol, mannitol, pentanetriol, pentaerythritol, diand tripentaerythritol, polyglycerol, dulcitol, inositol, carbohydrates, methyltrimethylolpropane, 2,6-octanediol, tetrahydroxycyclohexane, 2-ethylhexanetriol-1,2,6, glycerol methyl ether, glycerol allyl ether, polyvinyl alcohol and polyallyl alcohol, and mixtures thereof. Such polyepoxides may be exemplified by glycerol triglycidyl ether, mannitol tetraglycidyl ether, pentaerythritol tetraglycidyl ether and sorbitol tetraglycidyl ether.

Other polyepoxides include the polyepoxypolyhydroxy polyethers obtained by reacting, preferably in an alkaline medium, a polyhydric alcohol or polyhydric phenol with a polyepoxide, such as the reaction product of glycerol and bis(2,3-epoxypropyl) ether, the reaction product of sorbitol and bis(2,3-epoxy-2-methylpropyl)ether, the reaction product of pentaerythritol and 1,2-epoxy- 4,5-epoxypentane, and the reaction product of bis-phenol and bis(2,3-epoxy-2-methylpropyl)ether, the reaction product of resorcinol and bis(2,3-epoxypropyl)ether, and the reaction product of catechol and bis(2,3-epoxypropyl)ether.

A group of polymeric-type polyepoxides comprises the hydroxy-substituted polyepoxy polyethers obtained by reacting, preferably in an alkaline medium, a slight excess, e. g., .5 to 3 mol excess, of a halogen-containing epoxide as described above, with any of the aforedescribed polyhydric phenols, such as resorcinol, catechol, bis-phenol, bis(2,2'-dihydroxy-dinaphthyl)methane, and the like.

Other polymeric polyepoxides include the polymers and copolymers of the epoxy-containing monomers possessing at least one polymerizable ethylenic linkage. When this type of monomer is polymerized in the substantial absence of alkaline or acidic catalysts, such as in the presence of heat, oxygen, peroxy compounds, actinic light, and the like, they undergo addition polymerization at the multiple bond leaving the epoxy group unaffected. These monomers may be polymerized with themselves or with other ethylenically unsaturated -monorners, such as styrene, vinyl acetate, methacrylonitrile, acrylonitrile, vinyl chloride, vinylidene chloride, methyl acrylate, methyl methacrylate, diallyl phthalate, vinyl allyl phthalate, divinyl adipate, chloroallyl acetate, and vinyl methallyl pimelate. Illustrative examples of these polymers include poly(allyl 2,3-epoxypropyl ether), allyl 2,3-epoxypropyl etherstyrene copolymer, methallyl 3,4-epoxybutyl ether-allyl benzoate copolymer, poly(vinyl 2,3-expoxypropyl)ether, allyl glycidyl ether-vinyl acetate copolymer and poly(4- glycidyloxystyrene) Preferred polyepoxides to be used in treating the textile fabrics according to the process of the present invention comprise the members of the group consisting of diglycidyl ether, diglycidyl thioether, monomeric aliphatic polyepoxides containing a plurality of glycidyl radicals joined through oxygen or sulfur ether linkages to aliphatic hydrocarbon radicals, monomeric aromatic polyepoxides containing a plurality of glycidyl radicals joined through oxygen or sulfur ether linkages to mononuclear or polynuclear aromatic radicals, the polyepoxy-containing reaction product of an aliphatic polyhydric alcohol and epichlorohydrin, the polyepoxy-containing polymeric reaction product of an aromatic polyhydric phenol and epichlorohydrin, the polyepoxy-containing reaction product of an aliphatic polyhydric alcohol and a polyepoxide compound, the polyepoxy-containing reaction product of a polyhydric phenol and a polyepoxide compound, the polymers of epoxy-containing monomers possessing at least one polymerizable ethylenic linkage prepared in the absence of alkaline or acidic catalysts, and copolymers of the aforedescribed epoxy-containing monomers and at least one monomer containing a CH2=C= group prepared in the absence of alkaline or acidic catalysts.

Coming under special consideration, particularly because of the excellent non-chlorine retention and washability characteristics of the resulting crease-proof fabrics, are the polymers and copolymers of the aliphatic epoxycontaining monomers, and more particularly the glycidyl ethers of unsaturated aliphatic alcohols, such as allyl 1,3-glycidyl ether, vinyl 2,3-glycidyl ether, allyl 2,3- glycidyl ether, crotyl 2,3-epoxybutyl ether, 2-methyl-2- hexenyl 2,3-glycidyl ether, and the like. These polymers are preferably prepared by heating the monomer or monomers in bulk or in the presence of an inert solvent such as benzene in the presence of air or a peroxy catalyst, such as ditertiarybutyl peroxide, at temperatures ranging generally from 75 C. to 200 C.

The preparation of polymers of this type may be illustrated by the following example showing the preparation of poly(allyl glycidyl ether).

PREPARATION OF POLYMERS OF GLYCIDYL ETHERS POLYMER A About parts of allyl glycidyl ether was combined with an equal amount of benzene and the resulting mixture heated at 155 C. in the presence of 3% di-tertiarybutyl peroxide. The solvent and unreacted monomer were then removed by distillation. The poly(allyl glycidyl ether) obtained as the resulting product had a molecular weight of about 481-542 and an epoxide value of 0.50 eq./100 g. For convenience, this product will be referred to hereinafter as Polymer A.

Particularly preferred members of the above-described group comprise the polymers of the Z-alkenyl glycidyl ethers having a molecular weight between 300 and 1000 and an epoxy equivalency greater than 1.0, and preferably between 1.2 and 6.0.

Also demanding special interest, particularly because of the superior properties, such as the excellent nonchlorine retention properties, of the textile fabrics treated therewith, are the polyglycidyl polyethers of polyhydric alcohols obtained by reacting the polyhydric alcohol With epichlorohydrin, preferably in the presence of 031% to 5% by weight of an acid-acting compound, such as boron trifluoride, hydrofluoric acid, stannic chloride or 'stannic acid. This reaction is effected at about 50 C. to C. with the proportions of reactants being such that there is about one mole of epichlorohydrin for every equivalent of hydroxyl group in the polyhydric alcohol. The resulting chlorohydrin ether is then dehydrochlorinated by heating at about 50 C. to 125 C. with. a small, e. g., 10% stoichiometrical excess of a base, such as sodium aluminate.

The preparation of these preferred polyglycidyl ethers PREPARATION OF GLYCIDYL POLYETHERS OF POLYHYDRIC ALCOHOLS POLYETHER B About 276 parts (3 mols) of glycerol was mixed with 832 parts (9 mols) of epichlorohydrin. To this reaction mixture was added parts of diethyl ether solution containing about 4.5% boron trifluoride. The temperature of this mixture was between 50 C. and 75 C. for about 3 hours. About 370 parts of the resulting glycerol-epichlorohydrin condensate was dissolved in 900 parts of dioxane containing about 300 parts of sodium aluminate. While agitating, the reaction mixture was heated and refiuxed at 93 C. for 9 hours. After cooling to atmospheric temperature, the insoluble material was filtered from the reaction mixture and low boiling substances removed by distillation to a temperature of about 150 C. at mm. pressure. The polyglycidyl ether, in amount of 261 parts, was a pale yellow, viscous liquid. It had an epoxide value of 0.671 equivalent per 100 grams and the molecular weight was 324 as measured ebullioscopically in dioxane solution. The epoxy equivalency of this product was 2.13. For convenience, this product will be referred to hereinafter as Polyether B.

Particularly preferred members of this group comprise the glycidyl polyethers of aliphatic polyhydric alcohols containing from 2 to 10 carbon atoms and having from 2 to 6 hydroxyl groups and more preferably the alkane polyols containing from 2 to 8 carbon atoms and having from 2 to 6 hydroxyl groups. Such products preferably have an epoxy equivalency greater than 1.0, and still more preferably between 1.1 and 4 and a molecular weight between 300 and 1000.

Also of importance are the monomeric and polymeric glycidyl polyethers of dihydric phenols obtained by reacting epichlorohydrin with a dihydric phenol in an alkaline medium. The monomeric products of this type may be represented by the general formula wherein R represents a divalent hydrocarbon radical of the dihydric phenol. The polymeric products will generally not be a single simple molecule but will be a complex mixture of glycidyl polyethers of the general formula wherein R is a divalent hydrocarbon radical of the dihydric phenol and n is an integer of the series 0, 1, 2, 3, etc. While for any single molecule of the polyether n is an integer, the fact that the obtained polyether is a mixture of compounds causes the determined value of n to be an average which is not necessarily zero or a whole number. The polyethers may in some cases contain a very small :amount of material with one or both of the terminal gly- .cidyl radicals in hydrated form.

The aforedescribed preferred glycidyl polyethers of the 'dihydric phenols may be prepared by reacting the required proportions of the dihydric phenol and the epichlorohydrin in an alkaline medium. The desired alkalinity is obtained by adding basic substances, such as sodium or potassium hydroxide, preferably in stoichiometric excess to the epichlorohydrin. The reaction is preferably accomplished at temperatures within the range of from 50 C. to 150 'C. The heating is continued for several hours to effect the reaction and the product is then washed free of salt and base.

the dihydric phenols will be illustrated below.

PREPARATION OF GLYCIDY-L POLYETHERS 0F DIHYDRIC PHENOLS POLYETHER C About 2 mols of bis-phenol was dissolved in 10 mol of epichlorohydrin and 1 to 2% water added to the resulting mixture. The mixture was then brought to C. and 4 mols of solid sodium hydroxide added in small portions over a period of about 1 hour. During the addition, the temperature of the mixture was held at about C. to C. After the sodium hydroxide had been added, the water formed in the reaction and most of the epichlorohydrin was distilled off. The residue that remained was combined with an approximately equal amount of benzene and the mixture filtered to remove the salt. The benzene was then removed to yield a viscous liquid having a viscosity of about 150 poi'ses at 25 C. and a molecular weight of about 350 (measured ebullioscopically in ethylene dichloride). The product had an epoxy value of 0.50 eq./100 g., and an epoxy equivalency of 1.75. For convenience, this product will be referred to hereinafter as Polyether C.

POLYETHER D A solution consisting of 11.7 parts of water, 1.22 parts of sodium hydroxide, and 13.38 parts of bis-phenol was prepared by heating the mixture of ingredients to 70 C. and then cooling to 46 C. at which temperature 14.06 parts of epichlorohydrin was added while agitating the mixture. After 25 minutes had elapsed, there was added during an additional 15 minutes time a solution consisting of 5.62 parts of sodium hydroxide in 11.7 parts of water. This caused the temperature to rise to 63 C. Washing with water at 20 C. to 30 C. temperature was started 30 minutes later and continued for 4 /2 hours. The product was dried by heating to a final temperature of 140 C. in 80 minutes, and cooled rapidly. At room temperature, the product was an extremely viscous semisolid having a melting point of 27 C. by Durrans mercury method and a molecular weight of 483. The product had an, epoxy value of 0.40 eq./='100 g., and an epoxy equivalency of 1.9. For convenience, this product will be referred to as Polyether D.

POLYETHER B About 228 parts of bis-phenol and 84 parts sodium hydroxide as a 10% aqueous solution were combined and heated to about 45 C. whereupon 176 parts of epichlorohydrin was added rapidly. The temperature increased and remained at about 95 C. for 80 minutes. The mixture separated into a two-phase system and the aqueous layer is drawn off. The resinous layer that remained is washed with hot water and then drained and dried at C. The Durrans mercury method melting point of the resulting product is 52 C. and the molecular weight is about 710. The product has an epoxy value of 0.27 eq./1-00 g. and an epoxy equivalency of 1.9.

Particularly preferred members of the above-described group are the glycidyl polyethers of the dihydric phenols, and especially 2,2-bis(4-hydroxyphenyl)propane, having an epoxy equivalency between 1J1 and 2.0 and a molecular weight between 300 and 900. Particularly preferred are those having Durrans mercury method softening point below about 60 C.

The polyepoxides are preferably applied to the fabric in the form of a solution or dispersion in order to insure a proper distribution of the materials throughout the fibers of the fabric. Any liquid medium, such as water, aqueous emulsions, volatile or relatively volatile solvents, may be used in the preparation of these solutions. The liquid medium employed with the polyepoxides should have no pronounced solvent action on the fibers of the fabric being treated, though the use of a medium having a slight solvent action or latent solvent or swelling action upon the fibers is not excluded and may, in fact, be advantageous. Suitable solvents include ethyl alcohol, butyl alcohol, isopropyl alcohol, acetone, dioxane, diacetone alcohol, esters, ethers and ether esters of glycol and glycerol, ethylene dichloride, benzene, toluene, and the like, and mixtures thereof.

The more soluble polyepoxides, such as those of the aliphatic-type, are preferably employed in a water solution or a solution made up of water and other miscible components, such as the lower aliphatic alcohols, such as ethyl alcohol, isopropyl alcohol, methanol, and the like. Particularly preferred mediums of this type comprise water-alcohol mixtures having a weight ratio varying from 3:1 to 1:5.

The less soluble polyepoxides, such as the viscous liquid to solid glycidyl polyethers of the dihydric phenols described above, are preferably employed in a volatile solvent or in an aqueous emulsion. Emulsifying agents employed for this purpose are preferably those that are free of nitrogen and strong acidic groups, such as the monooleate of sorbitan polyoxyethylene, the trioleate of sorbitan polyoxyethylene, sorbitan tristearate, sorbitan monolaurate, polyoxyethylene ethers of alkylphenols, carboxymethylcellulose, starch, gum arabic, aryl and alkylated aryl sulfonates, such as cetyl sulfonate, oleyl sulfonate, sulfonated mineral oils, and the like, and mixtures thereof. The emulsifying agents are generally employed in amounts varying from 0.1% to 10% by weight and more preferably from 1% to by weight.

The amount of the polyepoxide in the impregnating solution may vary over a considerable range depending chiefly on the amount of resin to be deposited on the fabric and this in turn will depend on the number of applications and the pick-up allowed per application. When the solution is applied but once, with a 90% to 100% pick-up by weight of the fabric in the dry state, a concentration ranging from 3% to 25 by Weight will ordinarily suffice. If less than 80% pick-up is permitted, the concentration may in some cases go as high as 30% to 50%.

The hardening or curing agents may be added to the polyepoxide solution before it is applied to the fabric or it may be applied by spraying or other suitable methods to the fabric after it has been impregnated with the polyepoxide. The curing agents are preferably added to the solution before it is applied to the fabric. Preferred curing agents to be used include the acid and acid-acting curing agents, such as the organic and inorganic acids and anhydrides as citric acid, acetic acid, acetic acid anhydride, butyric acid, caproic acid, phthalic acid, phthalic acid anhydride, tartaric acid, aconitic acid, oxalic acid, succinic acid, succinic acid anhydride, lactic acid, maleic acid, maleic acid anhydride, fumaric acid, glutaconic acid, l,2,4-butanetricarboxylic acid, isophthalic acid, terephthalic acid, malonic acid, l,1,5-pentanetricarboxylic acid, acetoacetic acid, naphthalic acid, trimellitic acid, phosphoric acid, boric acid, sulfonic acid, phosphinic acid, perchloric acid, persulfuric acid, p-toluenesulfonic acid, ethanesulfonic acid, and the like compounds having at least one sulfonic group linked to a hydrocarbon radical. The boron-triiluoride complexes, such as the p-cresol and urea complex, may also used as hardening agents. The amino compounds, such as trietlryiarnine, ethylene diamine, and diethylene triamine may also be used but are less preferred. Particularly preferred curing agents comprise the organic carboxylic acids and inorganic acids and their correspo. anhydrides, and more preferably the organic monocarboxylic acids and polycarboxylic acids containing from 2 to 12 carbon atoms, and their respec tive anhydrides, and the inorganic acids containing sulfur, phosphorous or boron, such as boric acid, phosphoric acid and sulfonic acid.

The amount of the curing agent to be utilized will vary over a wide range depending upon the polyepoxide selected, the method of cure, etc. The organic acids and acid anhydrides are preferably added in an amount varying 0.1 to 2 times the stoichiometric amount, the stoichiometric quantity in this case being that amount sufiicient to furnish one carboxyl group for every epoxide group. Particularly amounts of organic acids and acid anhydrides vary from 0.2 to 1.5 times the stoichiometric amount. The inorganic acids are preferably employed in amounts varying from 0.5% to 20% by weight of the polyepoxide, and more preferably from 2% to 10% by weight. The boron-trifluoride complexes are generally employed in amounts varying from 0.25% to 5% and more preferably from 1% to 3% by weight.

The solutions employed to treat the textiles may also contain plasticizers to improve their flexibility, though these should not be present in such proportions as to render the finished materials soft or sticky at temperature and humidities to which they would be exposed. It is found, however, that the substances employed in the present invention yield products which are sufliciently flexible for most purposes without the use of plasticizers. Among plasticizers that may be used according to the present invention may be mentioned organic and inorganic derivatives of phenols, for example, diphenylol propane and triphenyl and tricresyl phosphates, sulphonamides, sulphonarylides, alkyl phthalates, for example, diethyl phthalate and glycol phthalates, diethyl tartrate, derivatives of polyhydric alcohols, for example, mono-, diand triacetin, and products obtained by condensing polyhydric alcohols with themselves or with aldehydes or ltetones. The compositions may also contain natural resins, e. g., shellac, rosin, and other natural resins and synthetic or semi-synthetic resins, e. g., ester gum, polyhydroxypolybasic alkyd resins, phenolaldehyde and urea-aldehyde resins.

Textile softening agents, and particularly those of the cationic-type as stearamidoethyl diethyl methyl quaternary ammonium methyl sulphate, trimethyl ammonium methyl sulphate of monostearylmetaphenylenediamine, s-di (1- (2-palmitamidoethyl)) urea monoacetate, palmityl amine hydrochloride, and the like, and mixtures thereof, may also be added in varying amounts to improve the feel of the treated fabrics.

The application of the solution containing the polyepoxide to the textile fabric may be eifected in any suitable manner, the method selected depending upon the results desired. If it is desired to apply the solution only to one surface of the material, as, for example, when it is desired to treat the back only of a fabric having a face of artificial or natural silk and a cotton back, the application may be effected by spraying or by means of rollers, or the composition may be spread upon the surface by means of a doctor blade. When, however, it is desired to coat both surfaces of the material, or if the material is to be thoroughly impregnated With it, the fabrics may be simply dipped in the solution or run through conventional-type padding rollers. The solutions may also be applied locally to the material, for example, by means of printing rollers or by stencilling.

The amount of the polyepoxides to be deposited on the fabric will vary over a wide range depending upon the degree of wrinkle-resistance and shrink-resistance desired in the finished material. if the fabric is to have a soft feel, such as that intended for use for dresses, shirts, etc., the amount of polyepoxide deposited will generally vary from 3% to 20% by weight of the fabric. If stiffer materials are required such as for shoe fabrics, draperies, etc. still higher amounts of resins, such as of the order of 25% to 50% by weight may be deposited. In determin ing the amount of resin deposited, it should, of course, be remembered that the presence of the polyepoxides in a few instances causes a slight decrease in tear strength of the fabric and the amount deposited should be balanced between the desired wrinkle resistance and the desired tear strength.

If the desired amount of the polyepoxide deposited in 9 the fabric is not obtained in one application, the solution can be applied again or as many times as desired in order to bring the amount of the polyepoxide up to the desired level.

. i Example] (a) About 100 parts of a glycidyl polyether of glycerol having an epoxy equivalency of 2.13 and a molecular After the desired amount of solution hasbeen applied Weight of about 324 (Polyether B described above) s to the fabric, the treated fabric is preferably dried for a dissolved in a solution made P of 140 Parts of P PY short period to remove some or all of the dispersing liquid, alcohol and 420 Parts of Water, and then Parts Of such as water, alcohol, and the like. This is generally citilic acid was added to the resulting Solutionaccomplished by exposing the Wet sheets to hot gas at y Cotton gingham (51113011t 80 X 70 count) cloth temperatures ranging f om 50 c, t 80 C, Th i d 1 was then impregnated with the above-described solution of drying will depend largely on the amount of pick-up y means of a Buttel'wol'th 3-1011 laboratory P permitted during the application of the solution, and the The 610th after Padding Showed a 65% Wet P P- The concentration of the polyepoxide. In most instances, impregnated 010th was then dried at r 15 m ndrying periods of from 5 to inut h ld b fli utes and cured at 160 C. for 5 minutes. The finished cient. 15 product was washed in a 0.13% solution of Ivory flakes The dried fabric is then exposed to relatively high temand 0.065% Na2CO3 solution at 70 C. for 12 minutes peratures to accelerate the cure of the polyepoxides, and then rinsed three times in warm water to remove any Temperatures used for this purpose generally range from lu l mat rials. 100 C. to 200 C., and more preferably from 100 C. The cloth treated in the above-described manner was to 150 C. At these preferred temperature ranges the 20 quite soft and had excellent wrinkle resistance, good tear cure can generally be accomplished in from 3 to 10 minand tensile strength, good washability and no chlorine utes. Exposures of less than 3 minutes, e. g. 1 minute, retention. Some of the properties of the cloth are shown may probably be used in continuous, commercial procin the table below in comparison to an unpadded sheet and essing. similar sheets treated with an urea-formaldehyde resin.

TABLE NO. I

Pementof $3313? 3;? 111 352322311 555 5523 1MEI-11+ Recovery Strength, Wrinkle 1n Tear Resm convem lbs. Recovery Strength ingagent Warp 1 111 Warp Fill Warp Fill Warp Fill Polyether B 5.21 107 100 2. 64 2.23 52.8 47.3 22.4 14. 5

Do 1.75 101 97 3.24 2.44 44.3 31.1 4.7 6.5- Urea-Formaldehyde 3.16 94 94 2.26 1.63 25.4 22.1 17.8 24. 2; none 70 74 3. 2.61

The process of the invention may be applied to the treatment of cellulosic fabrics as cotton fabric and fabric made 11p of regenerated cellulose (rayon) such as obtained by the viscose, cuprammonium or nitrocellulose process. While the invention has been particularly described with relation to the treatment of woven fabrics, it may also be applied to other materials, for example, knitted or netted fabrics.

The materials treated according to the process of the invention will have excellent wrinkle and shrink resistance as well as good resiliency and flexibility and may be used for a wide variety of important applications. The woven cotton, rayon and wool fabrics, both colored and white, containing conventional amounts of resin, e. g., from 3% to 25% by weight, may be used, for example, in the preparation of soft goods, such as dresses, shirts, coats, sheets, handkerchiefs, and the like, while the fabrics containing much larger amounts of the resin, 6. g., 25% to 50% may be used in other applications demanding more crispness and fullness such as the preparation of rugs, carpets, plushes, drapes, upholsteries, shoe fabrics, and the like.

To illustrate the manner in which the invention may be carried out, the following examples are given. It is to be understood, however, that the examples are for the purpose of illustration and the invention is not to be regarded as limited to any of the specific materials or conditions recited therein.

The wrinkle recovery values reported in the examples were determined by the Monsanto wrinkle recovery method, and the tear strength values were determined by the Trapezoid methodASTMD-3949. All tests were carried out at 50% relative humidity and 78 F.

Unless otherwise indicated, parts disclosed in the examples are parts by weight.

(b) The chlorine retention of the fabrics shown in (a) above was demonstrated in the following manner. The treated fabrics were first dipped for 10 minutes in a hypochlorite bleaching solution containing 0.4% available chlorine using a bath to cloth ratio of 301 and main tained at 140 F. They were then rinsed 6 times for 5 minutes at 100 F. and dried as smooth as possible. A hot iron at 400 F. was placed on the cloth for 30 seconds. The cloth was then examined to determine the discoloration of the spot under the iron and tested to determine amount of degradation. A dark color indicated charring due to chlorine retention. The results obtained in these tests are shown in the table below.

TABLE NO. II

Readings taken from Lumitrom using tri-g'reen filter-793 Standard white backing plate.

It can be seen from an examination of the data in Table II that the cloth treated with the Polyether B had a negligible if any chlorine retention and could be subjected to extensive bleach without fear of discoloration or strength loss during subsequent exposures to heat.

Example II (a) About 100 parts of poly(al1yl glycidyl ether) (Polymer A described above) was. dissolved in a solution I 11' made up of 140 parts of isopropyl alcohol and 420 parts of water, and then 40 parts of citric acid was added to the resulting solution.

Cotton print cloth (80 x 80 count) was then impregnated with this solution as shown in. Example I. The impregnated cloth was dried at 60 C. for 15 minutes and cured at 160 C. for 5 minutes. It was then washed as in Example I to remove any soluble material.

The cloth treated in the above-described manner had a 61% increase in wrinkle recovery.

(b) The treated fabric prepared in (a) above was washed at 70 C. for 12 minutes using a. 0.13% solution of Ivory flakes and .065 Na2CO3. The loss in Weight due to the washing is shown in the following table in comparison to similar results obtained by washing cotton print fabrics treated with urea-formaldehyde and me]- amine-formaldehyde, resins.

TABLE. NO. III

Example III A series of impregnating solutions containing Polyether B and a variety of different curing agents was prepared in the following manner: 100 parts of the polyether was dissolved in a solution made upof 140 parts of isopropyl alcohol and 420 parts of water and then the curing agent was added thereto.

Sheets of cotton print cloth were then impregnated with the individual solutions as indicated in Example I to give a 56% resin pick-up. The sheets were dried at 60 C. for 5 to 15 minutes and then cured at160 C. for 5 minutes.

The increase in wrinkle recovery of each of' the sheets are shown in the following table.

TABLE NO. IV

Increase in Amount of Percent Curing Agent Agent Wrinkle (PER) 1 Recovery warp Citric Acid 35. 9 33. 3 Tartaric Acid. 3S. 4- 26. 2 Aconitic Acid. 36. 5 25.0 Maleic Acid..- 29. 7 25.

Oxalic Acid- 23.0 31.0 Boric Acid 15.8 14. 3 Phosphoric Acid 19. 6 34.

1 Parts per hundred parts of resin.

Example IV In this experiment, the Polyether B-citric acid impregnating solution prepared in Example I and the Polymer A-citric acid solution shown in Example II were used to.

treat rayon gabardine cloth. This was accomplished by impregnating the cloth with the aforedescribed solutions by means of the Butterworth 3-roll laboratory padder (about 80% pick-up), drying the impregnated cloth at 60 C. for about 15 minutes and curing the cloth at- 160 C.

The rayon cloth treated in the above-described manner was quitesoft andhad increased wrinkle resistance, good washability and excellent shrink resistance. The wrinkle recovery is shown in the following table in comparison to an unp'added sheet and a similar sheet padded with an urea-formaldehyde resin.

TABLE NO. V

Wrinkle Recovery Example V This example illustrates the increase in tear strength that is obtained by using many of the polyepoxides described in the foregoing specification.

About parts of a diglycidyl ether of resorcinol having an epoxy value of .941 eq./ 100 g. was dissolved in 'a solution made up of parts of water and 420 parts isopropyl alcohol, and then about 3% by weight of a boron-trifluoride p-cresol complex was added to the resulting solution.

Cotton print cloth was then treated with the abovedescribed solution as shown in Example 1, dried at 60 C. and then cured at C. for 5 minutes. The finished sheets had a 14% increase in wrinkle resistance and a 14.3% increase in tear strength. The sheets also had improved washability and no chlorine retention.

Example VI About 100 parts of diglycidyl ether of ethylene glycol having an epoxy value of 1.039 eq./ 100 g. was dissolved in a solution made up of 140 parts of isopropyl alcohol and 420 parts of water, and then about 40 parts of citric acid was added.

Cotton print cloth treated with the above-described solution as indicated in Example V was soft and had increased wrinkle resistance, improved washability and no chlorine retention.

Example VII About 100'parts of a glycidyl polyether of bis-phenol having an epoxy equivalency of 1.75 and a molecular weight of about 350 (Polyether C produced above) was combined with 30 parts of citric acid and 10 parts of an emulsifying agent comprising a copolymer of ethylene oxide and propylene oxide (Pluronic F-68). This mixture was warmed to form a solution of the components and then cooled. Water was then added dropwise with gentle paddling unit the emulsion inverted. A further quantity of water was then added rapidly to form a solution having a 10% resin concentration.

Cotton print cloth described above was impregnated with the above-described emulsion by means of the Butterworth 3-roll laboratory padder. The cloth after padding: showed a 80% wet pick-up. The impregnated cloth was dried at 60 C. for 15 minutes and cured at 160 CI for 5 minutes. The resulting fabric had an increase in wrinkle resistance of 23.5% and a 35% decrease in tear strength.

Example VIII About 200 parts of a glycidyl polyether of bis-phenol having an epoxy equivalency of 1.9 and a molecular weight of 483 (Polyether'D produced above) is stirred with 2 parts of sorbitan monoleate (Span 20) and this mixture is then added to 200 parts of a 1% solution of a monooleate of sorbitan polyoxyethylene (Tween 80) and the resulting mixture stirred at full speed with the B'rookfield' 12,000 R. P. M. stirrer. 20 parts of citric acid isthen added to the resulting emulsion.

Cotton print cloth treated with the above-described emulsion as in the preceding example is soft and has increased wrinkle resistance, improved washability and low non-chlorine retention.

Example IX Crease resistant fabrics which were unusually soft and had a pleasant feed were obtained by the following procedure.

About 100 parts of Polyether B described above was dissolved in a solution made up of 140 parts of isopropyl alcohol and 420 parts of water, and then 40 parts of citric acid added to the solution. Aerotex Softener H (a mixed cationic and anionic long chain derivative) was then added to separate portions of the above-described solution in proportions indicated in the table below.

80 square cotton print cloth (80 x 80) was then impregnated with the above-described solutions by means of a Butterworth 3-roll laboratory padder. The cloth sheets were then dried at 60 C. for 15 minutes, cured at 160 C. for 5 minutes, and then washed as shown in Example I.

The treated sheets were very soft and had a pleasant feel but still had very good crease and shrink resistance. The wrinkle recovery values are shown in the following table.

TABLE NO. VI

Wrinkle Recovery Percent Softener Added Varp Fill 1 The softener in this case was added after the cloth had been treated with the polyepoxide and subsequently cured.

We claim as our invention:

1. A process for producing crease resistant and wrinkle resistant textile fabrics containing substantially all cellulosic material of the group consisting of cotton and rayon having a soft feel and improved resistance to washing and low chlorine retention which comprises impregnating the textile fabric with a Water-alcohol solution containing a saturated polyglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1.0 and a molecular weight between 300 and 900 and an acid curing agent, drying the composition for a short period, and then heating the composition at a temperature between 50 C. and 200 C. to cure the polyepoxide within the fibers of the said fabric.

2. The process as defined in claim 1 wherein the acid curing agent is citric acid.

3. The process as defined in claim 1 wherein the acid curing agent is phosphoric acid.

4. The process as defined in claim 1 wherein the fabric is cotton and the polyglycidyl ether is a glycidyl polyether of glycerol having an epoxy equivalency of about 11 to 3.0 and a molecular weight between 300 and 900.

5. The process as defined in claim 1 wherein the fabric is viscose rayon.

6. The process as defined in claim 1 wherein the acid curing catalyst is a member of the group consisting of acid or acid-acting curing agents.

7. A process for producing crease resistant and shrink resistant textile fabrics containing substantially all cellulosic material of the group consisting of cotton and rayon having a soft feel and improved washability and low chlorine retention which comprises impregnating the textile fabrics with an aqueous emulsion containing a saturated polyglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1.0, and an acid curing agent, and then heating the composition at a temperature between 50 C. and 200 C. to cure the polycpoxide within the fabric fibers.

8. A process for producing crease-resistant and shrinkresistant cellulosic textile fabrics containing substantially all cotton which comprises impregnating the textile fabric with an aqueous dispersion containing a glycidyl polyether of glycerol, having an epoxy equivalency of about 2 to 3 and a molecular weight between 300 and 900, and a curing agent, and then heating the treated fabric to cure the glycidyl polyether of glycerol within the treated fabric.

9. A process for producing crease-resistant and shrinkresistant textile fabrics containing substantially all cotton which comprises impregnating the textile fabric with an aqueous emulsion containing a saturated polyepoxy-containing dehydrochlorinated reaction product of an aliphatic polyhydric alcohol and epichlorohydrin which reaction product has an epoxy equivalency greater than 1.0, and a curing agent, and then heating the resulting treated fabric to cure the polyepoxy-containing reaction product within the treated fabric.

10. A process for treating textile materials containing substantially all cellulosic material selected from the group consisting of cotton and rayon to make them crease-resistant and shrink resistant without affecting feel and chlorine-retentive properties which comprises impregnating the textile material with an aqueous medium containing a saturated polyglycidyl ether of a polyhydric alcohol having an epoxy equivalency greater than 1.0, and a curing agent, and then heating the treated textile material to cure the polyglycidyl ether within the treated textile material.

11. A process as in claim 9 wherein the polyhydric alcohol is glycerol.

12. A process as in claim 9 wherein the polyhydric alcohol is diethylene glycol.

13. A process as in claim 9 wherein the curing agent is an acid-acting curing agent.

References Cited in the file of this patent UNITED STATES PATENTS 2,444,333 Castan June 29, 1948 2,494,295 Greenlee Jan. 10, 1950 2,511,913 Greenlee June 20, 1950 2,512,996 Bixler June 27, 1950 2,541,027 Bradley Feb. 13, 1951 2,589,245 Greenlee Mar. 18, 1952 2,606,810 Erickson Aug. 12, 1952 

1. A PROCESS FOR PRODUCING CREASE RESISTANT AND WRINKLE RESISTANT TEXTILE FABRICS CONTAINING SUBSTANTIALLY ALL CELLULOSIC MATERIAL OF THE GROUP CONSISTING OF COTTON AND RAYON HAVING A SOFT FEEL AND IMPROVED RESISTANCE TO WASHING AND LOW CHLORINE RETENTION WHICH COMPRISES IMPREGNATING THE TEXTILE FABRIC WITH A WATER-ALCOHOL SOLUTION CONTAINING A SATURATED POLYGLYCIDYL ETHER OF A POLYHYDRIC ALCOHOL HAVING AN EPOXY EQUIVALENCY GREATER THAN 1.0 AND A MOLECULAR WEIGHT BETWEEN 300 AND 900 AND AN ACID CURING AGENT, DRYING THE COMPOSITION FOR A SHORT PERIOD, AND THEN HEATING THE COMPOSITION AT A TEMPERATURE BETWEEN 50* C. AND 200* C. TO CURE THE POLYEPOXIDE WITHIN THE FIBERS OF THE SAID FABRIC. 